Dihydronordicyclopentadienyl mono-ethers of polyhydric alcohols



Patented Jan. 2c, 1946 UNITED STATES," PATENT OFFICE MoNO-ETHERS OF ALCOHOLS I PoLYnYnnrc Herman mm, Philadelphia, Pa., asslgnor to- The Resinous Products & Chemical Company, Philadelphia, Pa., a corporationoi. Delaware No Drawing. Application March 25, 1944, Serial No. 528,166

11 Claims.

This invention relates to addition-rearrangement products of polyhydric alcohols and dicyclopentadiene, said products being dihydronordicyclopentadienyl ethers of polyhydric alcohols. More particularly, this invention is concerned with the dihydronordicyclopentadienyl ,monoethers ofaliphatic polyhydric alcohols.

It is already known that ethers are obtained where dih'ydro-a-dicyclopentadiene is boiledwith alcohols in the ,presence of selenious acid as an.

oxidizing agent (Alder and Stein, Liebig's Annalen der Chemie, 504, pages 207-209 (1933)). These known ethers are derivative 01' dihydro-adicyclopentadiene-ol-3 and are formed as fol- In accordance with the present invention, however; instead oi. the dihydro derivative, dicyclopentadiene itself is condensed in the presence cl 9, non-oxidizing acidic condensing agent, for example, sulfuric acid or boron trifluoride, with a.

polyhydric alcohol whereby addition of one bydroxyl group of the polyhydric alcohol at the double bond 01 the bridged endomethylene cycle of the dicyclopentadiene occurs with a simultaneous molecular rearrangement of the latter to a hitherto unknown polycyclic ring system which,

for the sake of brevity, is herein termed the "nordicyclopentadiene ring ystem to distinguish it from the dicyclopentadiene ring system which is its precursor. The product obtained is a hydroxylated mono-ether of hydroxydihydronordicyclopentadiene and is formed in accordance with the following equation (using ethylene glycol as the simplest polyhydric alcohol), the formula for the isomers A or B representing the constitution 01' the product, of these A being the more probable:

n will be seen that the new ethers obtained according to the present invention difier Irom the Alder and Stein ether in being formed by direct addition of the components of the alcohol to the double bonds without the loss of a hydrogen atom from the dicyclopentadiene nucleus, in having the ether group attached to a different ring than in the Alder and Stein alcohol, and in having a new ring system, namely, the dihydronordicyclopentadienyl" ring system,'as shown in i formula (A) or (B) resulting from the complete transformaticn of the original dicycyopentadiene system. It will be noted that in the ,dihydronordicyclopentadienyl ethers obtained according to this invention, the ether oxygen atom is attached to an endoethylene cyclopentano group, forming one terminal cycle oi the new system through a CH- group flanked on one side by a CH: group and on the other by a tertiary carbon atom, whereas in the known ethers of dihydro-a-dlcyclopentadiene-ol-3 the ether oxygen atom is attached to a CH- group flanked by two secondary CH- groups, arrangements conferring entirely difl'erent chemical and physical properties to the respective ethers.

A most important chemical. property of the new hydroxy ethers produced according to the present invention is their unique tendency to absorb oxygen from the air. This property is even more accentuated when the free hydroxyl groups are esterified with ether unsaturated carboiwlic acids or polycarboxylic acids, the esters thus obtained being useful as synthetic drying oils. I

Instead of ethylene glycol, other polyhydric alcohols may be used for the purpose of this invention. They may possess chains or cycles which are interrupted by one or more oxygen atoms and they may contain non-interfering substituents such as halogen, nitro, thiocyano, cyano, aryl, aralkyl, alkyl, alkylene, alkoxy, aryloxy, or cycloalkyl groups. Typical polyhydric alcohols which may be employed for the purpose of this invention include. the alkylene glycols and polyalkylene glycols, for example, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, butylene glycol-1,2, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, octadecane 1,12-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, hexaethylene glycol, nonaethylene glycol and higher polyethylene glycols, glycerol, polyglycerols, glyceryl-a-ethyl ether, glyceryl-a-phenyl ether, glycerol monochlorhydrin, glycerol monobromhydrin, dihydroxypropionltrile, g 1y e r o l zinc chloride, stannic chloride, titaniumtetrachloride, antimonic chloride, aluminum chloride, ferric chloride, acidic siliceous clays such as those sold under the trade names of "Tonsil" or Atapulgas," etc.

As examples of the coordination complexes of boron tritluoride, there may be cited those with ethers, typified by BFaCzHaOCaI-Is and BFb.C4HaOC4Ho; with carboxylic acids,-typified by BFa.2CHaCOOH; with carboxylic esters, typified by BF:.2CH3COOC2H5; with ketones, typified by BFaCHsCOCHa; with alcohols, typified by BFa.2C4H9OH, and with water, which may be represented by BFaxI-lzOh, a: being usually one or two. a

The preferred catalysts are sulfuric acid and boron trifiuoride or its coordination complexes. It is surprising to note that, though even in traces these catalysts promote polymerization of monomeric cyclopentadiene to resins in the absence of an alcohol, and also polymerize unsaturated ethers in general, they do neither to any appreciable degree in the case of a mixture of dicyclopentadiene and the polyhydric alcohols as described herein, but on the contrary promote the formation of highly reactive and useful unsaturated ethers by an addition-rearrangement reaction.

In general, only' a small amount of. catalyst is required, quantities of from 0.5% to 5% on the weight of the reactants being usually sufficient although more may be used.

The quantity of dicyclopentadiene used is adhydric alcohol, the products then being mostly mono-ethers containing only one dihydronordicyclopentadienyl group. in the molecule together with smaller amounts of polyethers.

vantageously one mol or less per mol of poly- '(1 mol),

The addition-rearrangement reaction may be initiated by mixing the components and catalyst at temperatures even as low as 0 C. in some cases, or at room temperature, or at, elevated temperatures. While it is generally desirable to control the temperature at the start, the reaction may be accelerated or carried to completion more rapidly by continuing the reaction for a long time or by raising the temperature. Temperatures as high as C. to 150 C. may thus be used, the upper temperature being limited by the cracking tendency of the dicyclopentadiene to revert to monomeric cyclopentadiene. The reaction range of about 50 C. to 145 C. is generally useful, the best working range being 95 to C. The reaction may be controlled by the rate of mixing the reactants and by the use of a solvent or diluent, such as a hydrocarbon solvent, including petroleum ethers or petroleum naphthas, or chlorinated hydrocarbons such as carbon tetrachloride, ethylene dichloride, tetrachlorethane, and the like.

After the reaction has been carried to the de sired point, the acidic condensing agent is removed as by washing with water or neutralization with an alkali, or both. The reaction product may then be distilled in many cases or otherwise purified, as by treatment with decolorizing clay or carbon, stripping, extraction, etc.

The following examples illustrate this invention, it being understood that the term dihydronordicyclopentadienyl" refers to the new polycyclic radical, C1oH1a--, represented by the following general formula:

wherein Cal-I4 is a propenylene group which in conjunction with the two adjoining carbon atoms forms a cyclopenteno ring.

Example 1 (a) A mixture of 62 grams of ethylene glycol 132 rams puredicyclopentadiene (1 mol), and 25 grams of BF3.C2H5OC2H5 was stirred and gradually heated to 95 C. under a reflux condenser. After about fifteen minutes, an exothermal reaction set in which raised the temperature to 125 C. The mixture was heated at 95 C. for three hours after the exothermal reaction had subsided. It was then washed with hot water, neutralized with soda, dried, and distilled under reduced pressure. The p-hydroxyethoiwdihydronordicyclopentadiene distilled at 125-140 C./2 mm. as a colorless oil. The yield was 99 grams. Upon redistillation, it boiled at l52-154 C./l2 mm. and possessed the following constants: N 1.5105; d4? 1.085.

(b) Twenty grams of 95% sulfuric acid was added gradually to 93 grams of ethylene glycol while the mixture was cooled to 20 C. The solution was stirred'and 139 grams of technical 95% dicyclopentadiene was added dropwlse. The mixture was then heated at 60 C. for one hour and finally at 95 C. for two hours. The product was washed with hot dilute excess sodium hydroxide solution and the washed oil dried and distilled in vacuo. The ,B-hydroxyethoxydihydronordicyclopentadiene boiling between 110 and 120 C. at 1 mm. amounted to 115 grams.

Example 2 (a) A mixture of 106 grams of diethylene glycol and 132 grams of pure dicyclopentadiene was stirred at 60 C. and 25 grams of boron trifiuoridediethyl ether complex run in dropwise. The mixture was stirred for one hour at 60-l0. C., then for two and one-half hours at 70-80 0., and finally for two hours at 95 C. The product was then washed with hot water, followed by a soda wash and a final water wash, and was distilled under reduced pressure. The fraction boiling at 150-160 C./3 mm. was the desired fi-hydroxyethoxyethoxydihydronordicyclopentadiene:

The yield was 102 grams. Upon redistillation, it boiled at 154-158 C./3 mm. and possessed the following constants: N 1.5029; d4" 1.086.

(b) To a stirred solution of five grams of 98% sulfuric acid in 212 grams of diethylene glycol heated to 110 0., there was gradually added 280 grams of dicyclopentadiene. The mixture was then heated at 125 C. for four hours, washed with hot dilute sodium hydroxide solution, and the oil layer dried and distilled in vacuo.

There was obtained 252 grams of p-hydroxyethoxyethoxydihydronordicyclopentadiene above, together with 74 grams of the diether,

boiling at 240-250 C./l.5 mm., wherein CH13 represents the radical.

Example 3 distilled over at 175-185 C./2 mm. as a colorless viscous oil. The yield was 83 grams. Upon redlstillation, it boiled at 175-180 C./2 mm, and

possessed the following constants: N 1.5186; (14 1.136. 1

Example 4 To a stirred mixture of 152 grams of trimeth-' ylene glycol and fifteen grams of BFs.Q(C4l-In)2, there was added dropwise 280 grams of technical 95% dicyclopentadiene during the course of one hour while the reaction temperature .was maintained at 100-ll5 C. After all of the dicyclopentadiene had been. added, the mixture was stirred for six and one-half hours at 115 0., washed with hot dilute sodium hydroxide solution, dried; and distilled in vacuo. The 'y-hydroxypropyloxydihydronordicyclonentadiene,

HOCHZCMWIOHB is a colorless oil boiling at 135-140 C./2.5 mm. and possessing the constants N 1.5067; d4" 1.0653.

- Example 5 Dicyclopentadiene (204 grams) was added dropwise during one hour to a stirred heated mixture of ten grams of BF' :|.O(C2Hs)2 and 155 gra of glyceryl-mono-a-methyl other at 115-12 c. After all of-the dicyclopentadiene had been added,.

the mixture was stirred for six and one-half hours longer at 120 12'5 C. The product was washed with dilute sodium hydroxide solution, dried, and v Q distilled in vacuo.

The dihydronordicyclopentadienyl mono-ether of glycerol-mono-methyl ether,

.distilledover at 1 55-180 C./4 mm. Upon redistillation, the pure compound boiled at 145-148 C./2 mm. Th yield was 134 grams. It is a colorless oil having the constants N 1.4991; 414 1.0822.

About 100 grams of the di-(dihydronordicyclo- 1 pentadienyl) ether ot' glycerol,

dihydronordicyclopentadienyl tin.

was also obtained as apale yellow oil boiling at 215-220 C./2.5 mm.

Example 6 A mixture of 228 grams of propylene glycol and 12 grams of boron trifluoride-di-n-butyl ether complex, BF3.0(C4H9)2, was added dropwise during the course of fifteen minutes to 420 grams of stirred dicyclopentadiene heated to 95 0., during which time the temperature rose to 110 C. After all had been added, the mixture'was stirred and .heated at 110-115 C. for five and one-half hours, then washed with hot water and sodium 'hydrox-idesolution, washed again, dried, and distilled in vacuo.

The dihydronordicyclopentadienyl mono-ether of propylene glycol distilled over at 120-130 C./2

' mm. as a colorless oil in a yield of 369 grams.

Upon redistillation, the pure compound boiled at 117-120 .C./ 1.5 mm. and has the constants: N 1.0559; d 1.5035.

A higher boiling liquid fraction (200-220 (32/2 I mni.) amounting to 132 grams, was also obtained,

corresponding to the di-(dihydronordicyclopentadienyl) ether of propylene glycol,

To a stirred solution of 300 grams of triethylene glycolv and 10 grams oi BF3.O(C2H.5)2 heated to 0., there was added dropwise 290 grams of dicyclopentadiene during the course of fifty min utes, during which time the temperature rose spontaneously to 125 C. After all of the dicyclopentadiene had been added, the mixture was stirred at -l20 C for seven hours, then washed with hot water and with dilute sodium hydroxide solution, dried, and distilled in vacuo.

The desired dihydronordicyclopentadienyl oxy ethoxyethoxyethanol having the formula:

distilled over between 170 and 200 C./2 mm. as a pale yellow oil in a yield of 285 grams.

Upon redistillation, the pure compound boiled at 185-190 C./2 mm.

A higher boiling fraction,

also obtained, corresponding to the di-ether,

wherein CmHra represents the dihydronordicyclopentadienyl group.

Example 8 A mixture of 10 grams of dihydroxy-fluoboric acid, BF32H1O, and 291 grams or tetraethylene glycol was added-dropwise during the course of one and one-half hours to 420 grams of dicyclopentadiene while the mixture was stirred and the reaction temperature was maintained at 115 C. After all had been added, the mixture was stirred for three hours longer at 120 C., then washed with hot water and sodium hydroxide solution, dried, and distilled in vacuo.

' The dihydronordicyclopentadienyl mono-ether oi tetraethylene glycol,

distilled over between 205 and 250 C./2 mm. as

. a pale yellow oil in a yield of 262 grams. Upon redistillation, the pure compound boiled at 219'-224 C.f1.5 mm.

A higher boiling fraction (boiling point, 280-290 C./2 mm.) was also obtained, amounting to 94 grams and corresponding to the diether,

It is a pale yellow oil which, upon redistillation,

amounting to 105- grams, which distilled at 245-250 J2 mm. was

gave the pure compound boiling at 270-275 C./ 1.5 mm.

Ezrample 10 To a stirred solution of 221 grams of glycerol monochlorhydrin and three grams of boron triiluoride-dibutyl ether complex, BF:.O(C4H9)2, heated to C., there was gradually added dropwise 280 grams of dicyclopentadiene during the course of one hour while the reaction temperature was maintained at l02-108 C. After all of the dicyclopentadiene had been added, stirring was continued for seven hours at C. The product was then washed with asoaooo water, with dilute soda solution, finally again with water, then dried and distilled in vacuo.

The dihydronordlcyclopentadienyloxy-chloropropanol,

distilled over at -160 C./1 mm. as a colorless oil'in a yield of 237 grams. Upon redistillation, the pure compound boiled at C./2 mm. 3 and possessed the following constants: N 1.5181; dr m-49.

Example 11 A mixture consisting of 52.8 grams of pure dicyclopentadiene, 60 grams of 2-nitro-2-ethyl-propane-1,3-diol, and two grams of BFa.O(C4H9) was stirred at 5060 C. and gradually warmed to '80" C. After the mixture had been stirred for four hours at 80 C., the product was cooled, washed with dilute soda solution, then with water, and dried in vacuo. The residual oil, amounting to ac grams, was distilled in vacuo.

The dihydr inordicyclopentadienyl mono-ether of 2-nitro-2-ethyl-propane-1,3-diol,

distilled over at -l80 C./2.5 mm. as a pale yellow oil in a yield of 40 grams. Upon redistlllation, the pure compound boiled at 160-170 C./2 mm.

Example 12 dried, and distilled in vacuo.

The dihydronordicyclopentadienyl mono-ether oi phenoxy propanediol,

distilled at -200 C.'/1 mm. as a colorless oil in a yield of 125 grams. Upon redistillation, the pure compound boiled at 185-190 C./1 mm.

The hydroxylated mono-ethers of hydroxydihydronordi'cyclopentadlene are useful as solvents in printing inks and nitrocellulose lacquers, as intermediates for the preparation of resins and plastics, as plasticizers, as intermediates for soaps and wetting agents, as insecticides, and for many other purposes.

Chemically, they are very reactive, their residual double bond taking up halogen, thiocy nogen, and hydrogen. Their free hydroxyl groupings may be esterified with organic carboxylic acids or sulfuric acid to yield useful products. For example, their esters with oleic, maleic, linoleic, acrylic, and sebacic acids are autoxidizable materials capable of being utilized as varnishes.

This application is a continuation-impart of copending application Serial No. 476,640, February 20, 1943.

I claim:

1. An acid-catalyzed, addition-rearrangement product 01 one moi of a polyhydric alcohol and one mol of dicyclopentadiene, said product being a dihydronordicyclopentadienyl mono-ether of the polyhydric alcohol, in which the alcohol group is attached through oxygen to a secondary carbon atom which is flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group forming a cyclopenteno group therewith.

2. An acid-catalyzed, addition-rearrangement product of one mol of an aliphatic polyhydric alcohol and one mol of dicyclopentadiene, said product being a dihydronordicyclopentadienyl mono-ether of the polyhydric alcohol, in which the alcohol group is attached through oxygen to a secondary carbon atom which is flanked 'by a methylene group and a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group forming a cyclopenteno group therewith.

-3. An acid-catalyzed, addition-rearrangement product of one mol of ethylene glycol and one mole of dicyclopentadiene, said product being a dihydronordicyclopentadienyl mono-ether of ethylene glycol, in which the glycol group is joined through oxygen to a secondary carbon atom which is flanked by a methylene group and by a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group forming a cyclopenteno group therewith.

4. An 'acidecatalyzed, addition-rearrangement product of one mol of'diethylene'glycol and one mol of dicyclopentadiene, said product being a dihydronordicyclopentadienyl mono-ether of diethylene glycol, in which the glycol group is joined through oxygen to a secondary carbon atom which is flanked by a methylene group and by a tertiary carbon atom in an endoethylene cyclop'entano group carrying a propenylene group forming a cyclopenteno group therewith.

5. An acid-catalyzed, addition-rearrangement product of one mol of glycerol and one mol of dicyclopentadiene, said product being a dihydronordicyclopentadienyl mono-ether of glycerol, in which the glycerol group is joined through oxygen tov a secondary carbon atom which is flanked by a methylene groupand by a. tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group forming a cyolopenteno group therewith.

6. A method for preparing an acid-catalyzed, addition-rearrangement product of one mol of dicyclopentadiene and one mol or a polyhydric alcohol, said product being a dihydronordicyclopentadienyl mono-ether of the polyhydric alcohol, which comprises reacting by bringing togather at to 145 C. a polyhydric alcohol andsubstantially one molecular equivalent of dicyclopentadiene in the presence of an acidic condensing agent. c

'7. A method for preparing an acid-catalyzed, addition-rearrangement product 0! one mol of dicyclopentadiene and one mol of an aliphatic polyhydric alcohol, said product being a dihydronordicyclopentadienyl mono-ether of the polyhydric alcohol, whichcomprises reacting by bringing together at 0 to 145 C. an aliphatic polyhydric alcohol and substantially one molecular equivalent of dicyclopentadiene in the presence of an acidic condensing agent.

8. A method for preparing an acid-catalyzed, addition-rearrangement product of one mol of dicyclopentadiene and one mol of an aliphatic polyhydric alcohol, said product being a dihydronordicyclopentadienyl mono-ether of the polyhydric alcohol, which comprises reacting by bringmg together at 0 to 145 C. an aliphatic polyhydric alcohol and substantially one molecular equivalent of dicyclopentadiene in the presence of a boron trifluoride catalyst.

9.=A.method for preparing an acid-catalyzed, addition-rearrangement product of one mol or dicyclopentadiene and one mol of ethylene glycol, said product being a dihydronordicyclopentadienyl mono-ether of said ethylene glycol, which comprises reacting by bringing together at 0 to 145 C. ethylene glycol and substantially one molecular equivalent of dicyclopentadiene in the presence of a boron trifluoride catalyst.

10. A method for preparing an acid-catalyzed, addition-rearrangement product of one mol of dicyclopentadiene and one mol of diethyleneglycol, said product being a dihydronordicyclopentadienyl mono-ether of said diethylene glycol,

which comprises reacting by bringing together at 0 to 145 C. diethylene glycol and substantially one molecular equivalent of dicyclopentadiene in the presence of a boron trifluoride catalyst.

11. A method for preparing an acid-catalyzed, addition-rearrangement product or one mol of dicyclopentadiene and one mol of glycerol, said product being a dihydronordicyclopentadienyl mono-ether of said glycerol, which comprises reacting by bringing together ati)" to C.-glycerol and substantially one molecular equivalent of dicyclopentadiene in the presence of a boron trifluoride catalyst.

. HERMAN A. BRUSON. 

